WO1998049223A1

WO1998049223A1 - Method for producing cellulose shaped bodies

Info

Publication number: WO1998049223A1
Application number: PCT/AT1998/000108
Authority: WO
Inventors: Christian Schlossnikl; Siegfried Ambrosch; Heinrich Firgo; Peter Gspaltl
Original assignee: Lenzing Aktiengesellschaft
Priority date: 1997-04-25
Filing date: 1998-04-24
Publication date: 1998-11-05
Also published as: EP0977802A1; US6177035B1; ATA70597A; AT404731B; AU7012498A

Abstract

The invention relates to a method for producing cellulose flat sheets and cellulose membranes in the form of flat membranes. By this method, a solution of cellulose in an aqueous tertiary amino oxide is extruded by means of an extrusion die having an extrusion gap, the solution taking the shape of a sheet, and is passed via an air gap into a regenerating bath. The method is characterized in that an extrusion die having an extrusion gap at least 40 cm long is used.

Description

Process for the production of cellulosic moldings

The present invention relates to a process for producing cellulosic moldings, in particular flat films and cellulosic membranes in the form of flat membranes, a solution of cellulose in an aqueous tertiary amine oxide being extruded by means of an extrusion die which has an extrusion gap, the solution being shaped in the form of a film , and the solution is passed through an air gap into a precipitation bath.

From US Pat. No. 2,179,181 it is known that tertiary amine oxides can dissolve cellulose and that cellulosic shaped bodies such as fibers can be obtained from these solutions by precipitation. A method for producing such solutions is known for example from EP-N - 0356419. According to this publication, a suspension of cellulose in an aqueous tertiary amine oxide is first prepared. The amine oxide contains up to 40% by mass of water. The aqueous cellulose suspension is heated and water is drawn off under reduced pressure until the cellulose dissolves.

From DE-N - 28 44 163 it is known to lay an air gap or an air gap between the spinneret and the precipitation bath for the production of cellulose fibers in order to achieve a warping of the nozzle. This warping of the nozzles is necessary because after the formed spinning solution comes into contact with the aqueous precipitation bath, it is very difficult to stretch the threads. The fiber structure set in the air gap is fixed in the precipitation bath.

A process for the production of cellulosic threads is also known from DE-N-28 30 685, according to which a solution of cellulose in a tertiary amine oxide is formed into filaments in a warm state, the filaments are cooled with air and then introduced into a precipitation bath to precipitate the dissolved cellulose. The surface of the spun threads is further wetted with water to reduce their tendency to stick to adjacent threads. A device and a method for producing seamless tubular films is known from WO 93/13670. According to this known method, the cellulose solution is formed into a tube by an extrusion nozzle with an annular extrusion gap, which tube is pulled over a cylindrical mandrel and introduced into the precipitation bath. So that the extruded tube does not stick to the surface of the mandrel, its surface is covered with a film of water, so that the inside of the tube coagulates and slides over the cylindrical mandrel. The tubular films obtained have wet strengths of approximately 10 to 30 N / mm ² .

WO 95/07811 also describes an apparatus and a method for producing cellulosic tubular films.

WO 95/35340 describes a blowing process for the production of oriented cellulosic films, the cellulose solution being extruded downward into a precipitation bath via a film blowing nozzle and an air gap. It is mentioned that stretching transverse to the transport direction of the blown film can be achieved via the gas pressure in the interior of the blown film and that the ratio of mechanical longitudinal to transverse properties can be set.

EP-A-0 042 517 discloses the production of dialysis membranes by extrusion of the cellulose solution through nozzles with a length of 18 cm.

From DE-A - 195 15 137 it is known that when cellulosic flat films are produced by means of slot nozzles, the extruded film in the air gap undergoes considerable width shrinkage. This is undesirable and, in addition to an insufficient film width, leads to significant fluctuations in the film thickness of up to 150%. For this reason, DE-A-195 15 137 proposes, for the production of flat films, first of all to produce tubular films by means of an annular nozzle, which are then cut into flat films. A special film blowing device is used to produce the tubular films, with which the extruded tube is stretched in the air gap not only in the withdrawal direction but also in the transverse direction. This is achieved through an effective gas pressure inside the hose, which stretches the hose. A disadvantage of this method is the complicated structure of the device to be used. Furthermore, it is known to the person skilled in the art from the field of extrusion of thermoplastic polymers, such as, for example, polyethylene or polypropylene, that films with a substantially better thickness distribution transverse to the direction of extrusion can be achieved with flat dies than is possible with round dies.

In the case of cellulosic membranes, in particular in the form of flat membranes, i.e. Membranes made of a flat film, the permeability of the membranes is an essential property. To solve certain separation tasks, it is important to select membranes with permeability, pore size and pore structure that are optimized for the separation task.

Dialysis membranes made from regenerated cellulose in the form of flat films, tubular films or hollow fibers have been known for a long time, and the cellulose can be regenerated by the Cuoxam process, by the viscose process or by hydrolysis of cellulose acetate. Depending on the process used and the process conditions, membranes with different dialysis properties are obtained.

US Pat. No. 4,354,938 describes, for example, a process for the production of dialysis membranes by the viscose process, in which a tubular membrane is stretched between 40 and 120% before drying in the transverse direction by being inflated with air, which results in a membrane with an in Longitudinal and transverse direction leads to uniform orientation. When the dried membranes are transferred to the wet state, the membranes represented in this way are subject to shrinkage in the longitudinal and transverse directions of 0.5-10%. The ultrafiltration performances are in the range between 2.5 ml / m ² .h.mm Hg and 5.2 ml / m ² .h.mm Hg with a wet thickness of 184 μm to 45 μm.

In "Membranes and Membrane Processes" by E. Staude, 1992, VCH Verlagsges.mbH, on page 19 it is described that biaxial stretching of finished cellophane membranes leads to enlargement of the pores, whereas monoaxial stretching leads to a reduction in the effective pore diameter. However, the viscose process offers only limited possibilities for setting membrane properties in a targeted manner. Furthermore, the recovery of the chemicals resulting from this process, such as sodium sulfate and carbon disulfide, etc., is very complex.

It is the object of the present invention to provide a method for producing cellulosic flat films by extrusion of a heated solution of cellulose in a tertiary amine oxide, which does not have the disadvantages mentioned above. In particular, the complex step for producing tubular films is to be overcome.

It is a further object of the invention to provide a process for the production of cellulosic membranes in the form of flat membranes, by means of which membranes with permeability optimized for the separation task to be solved in each case can be obtained.

The process according to the invention for the production of cellulosic flat films and cellulosic membranes in the form of flat membranes, wherein a solution of cellulose in an aqueous tertiary amine oxide is extruded by means of an extrusion die which has an extrusion gap, the solution being shaped like a film, and the solution via an air gap is guided into a precipitation bath, characterized in that an extrusion die is used which has an extrusion gap with a length of at least 40 cm. This means that the extrudate, ie the solution shaped like a film, has a width of at least 40 cm as soon as it leaves the extrusion gap.

Surprisingly, it has been found that when the extrusion gap is extended to a value of at least 40 cm, the film obtained shrinks less than 20% in width during the further process steps. This slight shrinkage is not exceeded up to 3 times even when the film is stretched in the longitudinal direction. The disadvantages described in DE-A - 195 15 137 in the production of flat films by means of a flat die can thus be overcome if the extrusion gap is at least 40 cm long.

An extrusion die is preferably used which has an extrusion gap with a length of at least 60 cm. An advantageous embodiment of the method according to the invention is that the film-shaped solution is drawn off in the air gap in the extrusion direction at a speed which corresponds to 0.2 to 20 times the speed at which the film-shaped solution emerges from the extrusion gap.

The rate of withdrawal can thus be less than the rate of solution exit from the extrusion gap, e.g. in a ratio of 0.2: 1 to 0.9: 1 or greater than the rate at which the solution exits the extrusion gap, e.g. in a ratio of 2: 1 to 20: 1, preferably up to 10: 1. However, the film-shaped solution can also be drawn off at the same or approximately the same speed at which it is extruded.

A further advantageous embodiment of the method according to the invention is characterized in that the film-shaped solution is stretched in the air gap in the extrusion direction and / or transversely to the extrusion direction.

Furthermore, the film-shaped solution can be stretched in the precipitation bath transversely to the direction of extrusion.

Another embodiment consists of leading the flat film out of the precipitation bath and then stretching it transversely to the direction of extrusion.

The film-shaped solution can be stretched in the air gap transversely to the extrusion direction with the aid of driven conveyor belts, which extend from the underside of the nozzle to the surface of the precipitation bath on both sides of the nozzle, as a result of which they are constantly wetted with precipitant and avoid sticking to the formed solution becomes. Immediately after exiting the extrusion die, the solution is held on both side edges between two conveyor belts. The conveyor belts are inclined towards the surface of the precipitation bath, transport the formed solution through the air gap into the precipitation bath and thereby stretch the formed solution. The extent of the stretching naturally depends on the angle that the conveyor belts form with the precipitation bath surface. In an analogous manner, the film can also be stretched transversely to the transport direction in the precipitation bath or after the precipitation bath. Other mechanisms customary in the plastics industry are also suitable for this stretching, for example those in the production of biaxially oriented polypropylene.

Part of the loss of width due to transverse shrinkage of the film already takes place in the air gap between the nozzle outlet and the precipitation bath surface and is influenced by the length of the air gap.

In the method according to the invention, the air gap is expediently set to a length of at most 15 cm, in particular at most 3 cm.

The temperature of the cellulose solution during extrusion in the process according to the invention is best in the range from 80 ° C. to 120 ° C., in particular in the range from 85 ° C. to 95 ° C.

A further advantageous embodiment of the method according to the invention is characterized in that an extrusion die is used which has an extrusion gap with a width in the range from 50 μm and 2000 μm.

It has furthermore been found that advantageous results can be achieved with the process according to the invention in particular if, for the distribution of the cellulose solution in front of the extrusion die, distribution systems such as are customary in the plastics industry, in particular a "clothes hanger" type distribution system, are used. Such distribution systems are e.g. from "Kunststoffe" 86 (1996), pages 1132 ff (Carl Hanser Verlag, Munich).

The process according to the invention is further characterized in that flat films can be produced with a balanced ratio of the mechanical longitudinal and transverse properties. Furthermore, films with high longitudinal strengths with only slightly reduced transverse properties can also be produced. It has proven to be expedient to lead the film out of the precipitation bath and to wash it, the film possibly being prevented from shrinking at the same time.

N-methylmorpholine-N-oxide (NMMO) has proven particularly useful as a tertiary amine oxide.

It has also proven expedient to dry the film after washing and at the same time to prevent it from shrinking. Drum drying, hot air drying, drying using infrared rays and microwaves and suction drum drying are particularly suitable drying processes. When using drum drying, the film can easily be prevented from shrinking by means of attached, moving belts. Surprisingly, it has been shown that the strength values of the film can be increased by a tension occurring during the drying process.

The properties of the flat films produced according to the invention can be adapted to the respective intended use by subsequent coating. It is e.g. possible to make the film hydrophobic, to influence the electrostatic behavior and the dyeability, to change the abrasion resistance and to make the film sealable.

The advantages of the method according to the invention described above also apply in particular to the production according to the invention of cellulosic membranes in the form of flat membranes.

The permeability of the membrane and thus also its ultrafiltration rate (UFR) can be influenced in particular by the choice of the speed at which the film-like solution is drawn off in the air gap. It shows that a lower withdrawal speed increases the permeability and thus the ultrafiltration rate of the membrane. The permeability of the membrane is also changed by transverse stretching of the film-like solution or the film after entering the precipitation bath. Essential membrane properties can thus be controlled by the choice of the pull-off speed and by transverse stretching of the solution or the film. The cellulosic flat film produced according to the invention is biodegradable and compostable and is particularly suitable as packaging material for food and other products, as a material for garbage bags and carrier bags, as a ngrar film, as a diaper film, as a substrate for composites, as an office film, as a household film or as a membrane, and for the separation of substance mixtures.

Preferred examples of the invention are explained in more detail with the following examples. The cellulose solutions used were prepared by the process described in EP-N - 0 356 419. In all examples, the films were washed after cellulose cases and treated with glycerin (glycerol content in the dried film: about 15% by mass) and then - unless otherwise stated - dried in a tenter in which the films were fixed lengthways and crossways . The properties listed in the examples were determined on the dried films, the strength (lengthways and crossways) and the longitudinal or transverse elongation being determined in accordance with DIΝ 53457.

The ultrafiltration rate given in the examples is defined as the permeate volume passing through the membrane wall per unit of time, based on the membrane area and the test pressure.

ml

UFR = t.A.p h.m .mmHg

V = volume of liquid (permeate) [ml] t = time [h]

N = membrane area [m ² ] p = test pressure [mm Hg]

The specified diffuse permeabilities are obtained by plotting ln (cc ₀ ) against time from the slope of the straight line. , c. A _, In- - = - .R dtff -

c ₀ = initial concentration c _t = concentration at time t

A = membrane area [cm]

V = dialysis volume [cm]

P _diff = diffuse permeability [cm / min] t = time [min]

For direct comparison of the different membranes, all permeabilities were converted to a wet thickness of 75 μm, i.e. that the corresponding times to reach equilibrium were normalized to this thickness. If, for example, the equilibrium state of the NaCl dialysis was reached after 100 hours with a 200 μm thick membrane, this corresponds to a time of 100 x 75/200 = 37.5 hours for a 75 μm thick membrane.

example 1

A cellulose solution with a temperature of 85 ° C, containing 15.5% by mass of cellulose, 74.6% by mass of NMMO and 9.9% by weight of water, was by means of a flat die, which an extrusion gap with a length of 40 cm and a width of 300 microns, with a throughput of 37.8 kg / h through an air gap of 2 cm vertically down into a precipitation bath, consisting of 80 mass% water and 20 mass% NMMO, extruded.

The cellulose solution formed as a flat film emerged from the nozzle at an outlet speed of 4.2 m min and was drawn off at the same speed. This means that the flat film was not stretched in the longitudinal direction in the air gap. The film obtained had the following properties:

Width: 37.0 cm

Thickness: 67.0 μm

Strength (longitudinal): 224.1 N / mm ²

Strength (transverse): 165.1 N / mm ²

Elongation: 25.6%

Transverse elongation: 54.3%

2

UFR water 5.5 ml / h.m .mm

Pditr NaCl 4.2.10 ^"3 cm / min

P _diff NAOH 5.2.10 ^"3 cm / min

This example shows that the film, which had a width of 40 cm immediately after extrusion, only shrank by 3.0 cm. This is a width shrinkage of only 7.5%.

Example 2

The procedure was analogous to Example 1, but the cellulose solution used had a temperature of 110 ° C. and consisted of 13.8 mass% cellulose, 76.4 mass% NMMO and 9.8 mass% water, the extrusion gap of the flat die used being a width of 500 μm, the throughput was 75.6 kg / h, the air gap was 1 cm and the precipitation bath consisted of 98% by mass of water and 2% by mass of NMMO.

The exit speed was 5.0 m / min and the film was only pulled off at 90% of the exit speed.

The film obtained had the following properties: Width: 37.0 cm

Thickness: 69.0 μm

Strength (longitudinal): 229.0 N / mm ²

Strength (transverse): 148.9 N / mm ²

Elongation: 19.4%

Transverse elongation: 4.4%

UFR water: 6.1 ml / h.m .mm

Pdiff NaCl 4.8.10 ^"3 cm / min

P _diff NAOH 5.9.10 ^" cm / min

Example 3

The procedure was analogous to Example 1, except that the cellulose solution used consisted of 15.0% by weight of cellulose, 74.6% by weight of NMMO and 10.4% by weight of water, the extrusion gap of the flat die used being 300 μm wide, the throughput Was 37.8 kg / h and the air gap was 5 cm.

The exit speed was 4.2 m / min and the film was only pulled off at 40% of the exit speed. The film obtained had the following properties:

Width: 35.0 cm

Thickness: 82.0 μm

Strength (longitudinal): 171.0 N / mm ²

Strength (transverse): 121.8 N / mm ²

Elongation: 42.9%

Transverse elongation: 74.8%

UFR water 7.4 ml / h.m .mm

Pdi _ff NaCl 6.5.10 ^" cm / min

P _diff NAOH 7.0.10 ^"3 cm / min

This example shows that the film, which had a width of 40 cm immediately after extrusion, only shrank by 5 cm. This is a width shrinkage of only 12.5%.

Example 4

The procedure was analogous to Example 1, except that the cellulose solution used consisted of 14.6% by mass of cellulose, 75.6% by mass of NMMO and 9.8% by mass of water, the extension gap of the flat die used being 1000 μm wide, the throughput 113.4 kg / h betmg and the air gap was 2 cm.

The exit speed was 3.8 m / min and the film was pulled off at three times the exit speed. The film obtained had the following properties:

Width: 35.0 cm Thickness: 92.0 μm

Strength (longitudinal): 218.4 N / mm ² Strength (transverse): 122.5 N / mm ² Longitudinal stretch: 27.1% Cross stretch: 87.3% UFR water 3.8 ml / hm .mm Hg Pdiff NaCl 2.0.10 ^{" 3} cm / min P _diff NAOH 2.6.10 ^"3 cm / min

This example shows that the film, which had a width of 40 cm immediately after extraction, only shrank by 5.0 cm. This is a width shrinkage of only 12.5%.

Example 5

A cellulose solution with a temperature of 85 ° C, containing 13.0% by mass of cellulose, 77.1% by mass of NMMO and 9.9% by mass of water, was by means of a flat nozzle, which an Extmsionspalt with a length of 40 cm and a width of 300 microns, with a throughput of 37.8 kg / h through an air gap of 2 cm vertically down into a precipitation bath, consisting of 80 mass% water and 20 mass% NMMO, extruded.

The exit speed was 4.2 m / min and the film was removed at the same speed. This means that the flat film was not stretched in the longitudinal direction. The film obtained had the following properties:

Width: 36.0 cm

Thickness: 80.0 μm

Strength (longitudinal): 144.0 N / mm ²

Strength (transverse): 115.9 N / mm ²

Elongation: 35.5%

Transverse elongation: 26.5%

2

UFR water 5.7 ml / h.m .mm

Pdiff NaCl 4,4.10 ^"3 cm / min

P _diff NAOH 5.1.10 ^" cm / min

This example shows that the film, which had a width of 40 cm immediately after extension, only shrank by 4.0 cm. This is a 10% width shrinkage.

Example 6

A cellulose solution with a temperature of 85 ° C, containing 14.2% by mass of cellulose, 76.3% by mass of NMMO and 9.5% by weight of water, was by means of a flat nozzle, which an Extmsionspalt with a length of 40 cm and a width of 100 microns, with a throughput of 75.6 kg / h through an air gap of 2 cm vertically down into a coagulation bath consisting of 80 mass% water and 20 mass% NMMO.

The exit speed was 25.0 m / min and the film was pulled off at three times the speed. The film obtained had the following properties:

Width: 33.0 cm

Thickness: 15.0 μm

Strength (longitudinal): 226.2 N / mm ²

Strength (transverse): 46.3 N / mm ²

Elongation: 11.3%

Transverse elongation: 35.0%

UFR water: 2.4 ml / hm ² .mm

Pdiff NaCl 1.1.10 ^" cm / min

P _diff NAOH 1, 4.10 ^"3 cm / min

This example shows that the film, which had a width of 40 cm immediately after extrusion, only shrank by 7.0 cm. This is a width shrinkage of only 17.5%.

Example 7

A cellulose solution with a temperature of 85 ° C, containing 14.1% by mass of cellulose, 75.6% by mass of NMMO and 10.3% by weight of water, was by means of a flat nozzle, which has an extraction gap with a length of 40 cm and a width of 1000 μm, with a throughput of 75.6 kg / h through an air gap of 5 cm vertically down into a coagulation bath consisting of 80 mass% water and 20 mass% NMMO.

The exit speed was 2.5 m / min and the film was removed at 2.2 times the speed. The film obtained had the following properties:

Width: 34.0 cm

Thickness: 135.0 μm

Strength (longitudinal): 193.9 N / mm ²

Strength (transverse): 130.5 N / mm ²

Elongation: 39.6%

Transverse elongation: 71.7%

UFR water 4.2 ml / h.m .mm Hg

Pdiff NaCl 2.1.10 ^" cm / min P _diff NAOH 3.1.10 ^" cm / min

This example shows that the film, which had a width of 40 cm immediately after extrusion, only shrank by around 6 cm. This is a widespread contraction of only 15%.

Example 8

A cellulose solution with a temperature of 110 ° C, containing 14.3 mass% cellulose, 76.2 mass% NMMO and 9.5 mass% water, was by means of a flat nozzle, which has an extraction gap with a length of 40 cm and a width of 500 μm, with a throughput of 75.6 kg / h through an air gap of 1 cm vertically down into a precipitation bath consisting of 98% by mass water and 2% by mass NMMO.

The exit speed was 5.0 m / min and the film was pulled off at 2.9 times the speed. The film obtained had the following properties:

Width: 35.0 cm

Thickness: .85.0 μm

Strength (longitudinal): 222.6 N / mm ²

Strength (transverse): 117.6 N / mm ²

Elongation: 20.9%

Transverse elongation: 32.2%

UFR water: 3.8 ml h.m .mm

P _d iff NaCl 1.9.10 ^" cm / min

P _diff NAOH 2.4.10 ^"3 cm / min

Example 9

A cellulose solution with a temperature of 110 ° C, containing 14.2% by mass of cellulose, 76.2% by mass of NMMO and 9.6% by mass of water, was by means of a flat nozzle, which has an extraction gap with a length of 40 cm and a width of 500 microns, with a throughput of 75.6 kg / h through an air gap of 3 cm vertically down into a precipitation bath consisting of 98 mass% water and 2 mass% NMMO.

The exit speed was 5.0 m / min, and the film was drawn off at 3 times the speed and stretched in the coagulation bath by 50% in the direction of its width (cross-stretched). The film obtained had the following properties:

Width: 55.0 cm

Thickness: 33.0 μm

Strength (longitudinal): 151.3 N / mm ²

Strength (transverse): 135.6 N / mm ²

Elongation: 16.4%

Transverse elongation: 37.3%

2

UFR water: 4.7 ml / h.m .mm

Pdiff NaCl 2.4.10 ^"3 cm / min

P _diff NAOH 2.6.10 ^"3 cm / min

Example 10

A cellulose solution with a temperature of 85 ° C, containing 14.6% by mass of cellulose, 75.9% by mass of NMMO and 9.5% by weight of water, was by means of a flat nozzle, which has an extraction gap with a length of 40 cm and a width of 300 μm, with a throughput of 37.8 kg / h through an air gap of 3 cm vertically down into a coagulation bath consisting of 80 mass% water and 20 mass% NMMO.

The exit speed was 4.2 m / min and the film was removed at the same speed. This means that the flat film was not stretched in the longitudinal direction in the air gap. However, the film was stretched in the air gap in the direction of its width by 10% (cross-stretched). The film obtained had the following properties:

Width: 40.0 cm

Thickness: 95.0 μm

Strength (longitudinal): 153.4 N / mm ²

Strength (transverse): 105.2 N / mm ²

Elongation: 49.8%

Transverse elongation: 71.7%

UFR water: 5.2 ml / hm ² .mm Hg

P _d i _ff NaCl 4.0.10 ^"3 cm / min

P _diff NAOH 4.9.10 ^"3 cm / min

Example 11

A cellulose solution with a temperature of 110 ° C, containing 14.2% by mass of cellulose, 76.2% by mass of NMMO and 9.6% by mass of water, was by means of a flat nozzle, which has an extraction gap with a length of 40 cm and a width of 500 μm, with a throughput of 75.6 kg / h through an air gap of 1 cm vertically down into a precipitation bath consisting of 98% by mass water and 2% by mass NMMO.

The exit speed was 5.0 m / min and the film was removed at the same speed.

The film obtained had the following properties:

Width: 37.0 cm Thickness: 85.0 μm Strength (longitudinal): 144.7 N / mm ² Strength (transverse): 95.0 N / mm ² Longitudinal elongation: 24.9% Cross elongation: 31.4% UFR water: ^■ 5.9 ml / hm ² .mm Hg P _d i _ff NaCl 4.5.10 ^"3 cm / min P _diff NAOH 5.5.10 ^"3 cm / min

Example 12

The procedure was analogous to Example 11, but the cellulose solution had a temperature of 95 ° C.

The film obtained had the following properties:

Width: 37.0 cm Thickness: 85.0 μm

Strength (longitudinal): 171.2 N / mm ² Strength (transverse): 117.0 N / mm ² Longitudinal stretch: 34.7% Cross stretch: 77.7% UFR water: 5.8 ml / hm ² .mm Hg P _d i _ff NaCl 4.5.10 ^"3 cm / min P _diff NAOH 5.4.10 ^{" 3} cm / min This example shows that the film, which had a width of 40 cm immediately after extrusion, only shrank by 3.0 cm. This is a widespread contraction of only 7.5%.

Example 13

The procedure was analogous to Example 1, but the temperature of the cellulose solution used was 110 ° C. and consisted of 13.8 mass% cellulose, 76.4 mass% NMMO and 9.8 mass% water, the extrusion gap of the flat die used being one length of 40 cm and a width of 500 microns and the throughput 75.6 kg / h betmg and the precipitation bath consisted of 98 mass% water and 2 mass% NMMO.

The exit speed was 5.0 m / min and the film was removed at the same speed. After the precipitation bath, the film was stretched by 54% in its width direction (cross-stretched).

The film obtained had the following properties:

Width: 56.0 cm

Thickness: 68.0 μm

Strength (longitudinal): 132.7 N / mm ²

Strength (transverse): 157.0 N / mm ²

Elongation: 40.9%

Transverse elongation: 36.1%

UFR water: 6.0 ml / hm ² .mm Hg

P _diff NaCl 4.6.10 ^"3 cm / min

P _diff NAOH 5.4.10 ^"3 cm / min Example 14

The procedure was analogous to that of Example 13, but the film was removed at 3 times its exit speed after extension.

The film obtained had the following properties:

Width: 55.0 cm

Thickness: 28.0 μm

Strength (longitudinal): 159.1 N / mm ²

Strength (transverse): 127.1 N / mm ²

Elongation: 29.1%

Transverse elongation: 74.8%

UFR water: 5.0 ml / hm ² .mm Hg

Pdiff NaCl 2.5.10 ^"3 cm / min P _diff NAOH 2.8.10 ^{" 3} cm / min

Example 15

A cellulose solution with a temperature of 85 ° C, containing 14.2% by mass of cellulose, 76.3% by mass of NMMO and 9.5% by weight of water, was by means of a flat nozzle, which has an extraction gap with a length of 40 cm and a width of 500 μm, with a throughput of 75.6 kg / h through an air gap of 1 cm vertically down into a precipitation bath consisting of 98% by mass water and 2% by mass NMMO.

The exit speed was 5.0 m / min and the film was removed at the same speed. After the precipitation bath, the film was stretched (cross-stretched) by 100% in its width direction. The film obtained had the following properties:

Width: 74.0 cm

Thickness: 45.0 μm

Strength (longitudinal): 119.1 N / mm ²

Strength (transverse): 184.6 N / mm ²

Elongation: 42.0%

Transverse elongation: 32.0%

UFR water 6.1 ml / hm ² .mm Hg

Pdiff NaCl 4.8.10 ^"3 cm / min P _diff NAOH 5.7.10 ^{" 3} cm / min

Example 16

A cellulose solution with a temperature of 110 ° C, containing 14.2% by mass of cellulose, 76.3% by mass of NMMO and 9.5% by weight of water, was by means of a flat nozzle, which has an extraction gap with a length of 40 cm and a width of 500 μm, with a throughput of 75.6 kg / h through an air gap of 1 cm vertically down into a precipitation bath consisting of 98% by mass water and 2% by mass NMMO.

The exit speed was 5.0 m / min and the film was removed at 3 times this speed. After the precipitation bath, the film was stretched by 100% in its width direction (cross-stretched).

The film obtained had the following properties:

Width: 72.0 cm Thickness: 17.0 μm Strength (longitudinal): 170.4 N / mm ² strength (transverse): 152.6 N / mm ² elongation: 26.9% transverse elongation: 44.7% UFR water: 5.1 ml / hm ² .mm Hg

Pdiff NaCl 2.9.10 ^"3 cm / min P _diff NAOH 3.1.10 ^" cm / min

Example 17

A cellulose solution with a temperature of 85 ° C, containing 14.1% by mass of cellulose, 75.6% by mass of NMMO and 10.3% by weight of water, was by means of a flat nozzle, which has an extraction gap with a length of 40 cm and a width of Extruded at a throughput of 189.0 kg / h through an air gap of 3 cm vertically down into a precipitation bath consisting of 80% by mass water and 20% by mass NMMO.

The cellulose solution formed as a flat film emerged from the nozzle at an exit speed of 6.3 m / min and was drawn off at the same speed. This means that the flat film was not stretched in the longitudinal direction in the air gap.

The film obtained had the following properties:

Width: 37.0 cm Thickness: 110.0 μm

Strength (longitudinal): 186.7 N / mm ² Strength (transverse): 118.1 N / mm ² Elongation: 32.3% Transverse elongation: 81.1% UFR water: 6.1 ml / hm ² .mm Hg Pdiff NaCl 4.5.10 ^"3 cm / min P _diff NAOH 6.6.10 ^" cm / min

Example 18

A cellulose solution with a temperature of 85 ° C, containing 14.6% by mass of cellulose, 75.9% by mass of NMMO and 9.5% by weight of water, was by means of a flat nozzle, which has an extraction gap with a length of 40 cm and a width of 300 microns, with a throughput of 37.8 kg / h through an air gap of 2 cm vertically down into a precipitation bath, consisting of 80 mass% water and 20 mass% NMMO, extruded.

The cellulose solution formed as a flat film emerged from the nozzle at an outlet speed of 4.2 m / min and was drawn off at 3 times this speed.

The film obtained had the following properties:

Width: 36.5 cm Thickness: 33.3 μm

Strength (longitudinal): 243.3 N / mm ² Strength (transverse): 92.3 N / mm ² Longitudinal stretch: 20.5% Cross stretch: 113.8% UFR water: 3.6 ml / hm ² .mm Hg P _d i _ff NaCl 1.6.10 ^'3 cm / min P _diff NAOH 2.3.10 ^"3 cm / min Example 19

A film was produced analogously to Example 18. This film was dried by means of a drum dryer, whereby it was pressed at the edges by moving belts onto the drum of the dryer and was thereby prevented from shrinking as a result of the drying.

The dried film obtained had the following properties:

Width: 36.5 cm

Thickness: 29.3 μm

Strength (longitudinal): 321.5 N / mm ² -

Strength (transverse): 108.8 N / mm ²

Elongation: 10.0%

Transverse elongation: 18.2%

Example 20 (comparison)

A cellulose solution with a temperature of 85 ° C, containing 14.6% by mass of cellulose, 75.9% by mass of NMMO and 9.5% by weight of water, was by means of a flat nozzle, which has an extraction gap with a length of 6 cm and a width of 300 μm, with a throughput of 11.4 kg / h through an air gap of 2 cm vertically down into a coagulation bath consisting of 80 mass% water and 20 mass% NMMO.

The cellulose solution formed as a flat film emerged from the nozzle at an exit speed of 8.3 m / min and was drawn off at the same speed. The film obtained had the following properties:

Width: 4.5 cm

Thickness: 89.0 μm

Strength (longitudinal): 154.4 N / mm ²

Elongation: 17.4%

The breadth of shrinkage in this case is 25%.

Example 21 (comparison)

The procedure was analogous to Example 20, but the air gap was set at 5 cm.

The film obtained had the following properties:

Width: 4.0 cm

Thickness: 85.0 μm

Strength (longitudinal): 126.5 N / mm ²

Elongation: 27.0%

The width shrinkage in this case is 33%.

Example 22

A cellulose solution with a temperature of 110 ° C. containing 14.2% by mass of cellulose, 76.3% by mass of NMMO and 9.5% by weight of water was produced using a flat die which had an extraction gap with a length of 40 cm and a width of 500 μm exhibited with one Throughput of 75.6 kg / h extruded vertically downwards through an air gap of 1 cm into a precipitation bath consisting of 98 mass% water and 2 mass% NMMO.

The cellulose solution formed as a flat film emerged from the nozzle at an exit speed of 5.0 m / min and was drawn off at a rate which was 10 times this speed.

The film obtained had the following properties:

Width: 19.0 cm

Thickness: 5.0 μm

Strength (longitudinal): 324.5 N / mm ²

Strength (transverse): 64.2 N / mm ²

Elongation: 10.8%

Transverse elongation: 63.4%

UFR water: 1.1 ml / hm ² .mm Hg

Pdiff NaCl 6.7.10 cm / min P _diff NAOH 9.2.1G ^"4 cm / min

Example 23 (comparison)

The procedure was analogous to Example 22, but the cellulose solution had 14.6% by mass of cellulose, 76.1% by mass of NMMO and 9.3% by weight of water and the flat die had an extraction gap with a length of 6 cm. The film obtained had the following properties:

Width: 1.68 cm

Thickness: 5.0 μm

Strength (longitudinal): 309.8 N / mm ²

Elongation: 9.1%

Example 24

A cellulose solution with a temperature of 90 ° C., containing 14.6% by mass of cellulose, 76.1% by mass of NMMO and 9.3% by weight of water, was introduced by means of a flat nozzle which had an extraction gap with a length of 40 cm and a width of 300 microns, with a throughput of 37.8 kg / h through an air gap of 2 cm vertically down into a precipitation bath, consisting of 80 mass% water and 20 mass% NMMO, extruded.

The exit speed of the cellulose solution formed as a flat film was 4.2 m / min, and the film was drawn off at the same speed. This means that the film was not stretched in the longitudinal direction.

The film obtained had the following properties:

Width: 37.0 cm

Thickness: 70.0 μm

Strength (longitudinal): 197.7 N / mm ²

Strength (transverse): 95.5 N / mm ²

Elongation: 52.5% Transverse elongation: 90.3% UFR water: 5.6 ml / hm ² .mm Hg

P _d i _ff NaCl 4.4.10 ^"3 cm / min

P _diff NAOH 5.3.10 ^" cm min

This example shows that the film, which had a width of 40 cm immediately after extraction, only shrank by 3.0 cm. This is a width shrinkage of only 7.5%.

Example 25

The procedure was analogous to Example 24, but the air gap had a length of 5 cm.

The film obtained had the following properties:

Width: 35.0 cm

Thickness: 73.0 μm

Strength (longitudinal): 172.7 N / mm ²

Strength (transverse): 101.3 N / mm ²

Elongation: 33.3%

Transverse elongation: 41.5%

UFR water: 5.5 ml / hm ² .mm Hg

Pdiff NaCl 4.5.10 ^"3 cm min P _diff NAOH 5.2.10 ^{" 3} cm / min

This example shows that the film, which had a width of 40 cm immediately after extrusion, shrank by 5.0 cm. This is a widespread contraction of 12.5%.

Claims

Claims:

1. A process for the production of cellulosic flat films and cellulosic membranes in the form of flat membranes, wherein a solution of cellulose in an aqueous tertiary amine oxide is extruded by means of an extrusion nozzle which has an extrusion gap, the solution being shaped like a film, and the solution via an air gap is led into a precipitation bath,

characterized in that

an extrusion die is used which has an extrusion gap with a length of at least 40 cm.

2. The method according spoke 1, characterized in that an extrusion die is used which has an extrusion gap with a length of at least 60 cm.

3. The method according to any one of claims 1 or 2, characterized in that the film-shaped solution is drawn off in the air gap in the extrusion direction at a speed which corresponds to 0.2 to 20 times the speed at which the film-shaped solution emerges from the extrusion gap .

4. The method according to any one of claims 1 to 3, characterized in that the film-shaped solution is stretched in the air gap in the direction of extrusion and / or transverse to the direction of extrusion.

5. The method according to any one of claims 1 to 4, characterized in that the film-shaped solution is stretched transversely to the direction of extrusion in the precipitation bath.

6. The method according to any one of claims 1 to 5, characterized in that the flat film is guided out of the precipitation bath and then stretched transversely to the direction of extrusion.

7. The method according to any one of claims 1 to 6, characterized in that the air gap has a maximum length of 15 cm.

8. The method according spoke 7, characterized in that the air gap has a maximum length of 3 cm.

9. The method according to any one of claims 1 to 8, characterized in that the temperature of the cellulose solution in the extrusion is in the range of 80 ° C and 120 ° C.

10. The method according spoke 9, characterized in that the temperature of the cellulose solution during extrusion is in the range from 85 ° C to 95 ° C.

11. The method according to any one of claims 1 to 10, characterized in that an extrusion die is used which has an extrusion gap with a width in the range of 50 microns to 2000 microns.

12. The method according to any one of claims 1 to 11, characterized in that the film is guided out of the precipitation bath and washed, the film being prevented from shrinking.

13. The method according to any one of claims 1 to 12, characterized in that N-methylmorpholine-N-oxide is used as the tertiary amine oxide.

14. The method according to any one of claims 1 to 13, characterized in that the film is dried after washing, the film being prevented from shrinking.

15. The method according to any one of claims 1 to 14 for the production of a cellulosic membrane, characterized in that the permeability of the membrane is controlled by the speed of the removal of the film-shaped solution in the air gap.

16. The method according to any one of claims 1 to 15 for the production of a cellulosic membrane, characterized in that the permeability of the membrane is controlled by transverse stretching of the film-shaped solution or the film after entering the precipitation bath.

17. Use of a cellulosic flat film, which was produced by a process according to one of claims 1 to 14, as packaging material for food and other products, as material for garbage bags and carrier bags, as agricultural film, as diaper film, as a substrate for composites, as office film, as household foil or as membrane, and for the separation of substance mixtures.